JP2742860B2 - ヒドロホルミル化触媒の再活性化 - Google Patents

ヒドロホルミル化触媒の再活性化

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Publication number
JP2742860B2
JP2742860B2 JP5026003A JP2600393A JP2742860B2 JP 2742860 B2 JP2742860 B2 JP 2742860B2 JP 5026003 A JP5026003 A JP 5026003A JP 2600393 A JP2600393 A JP 2600393A JP 2742860 B2 JP2742860 B2 JP 2742860B2
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Japan
Prior art keywords
hydroformylation
rhodium
catalyst
tertiary
complex
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Expired - Lifetime
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JP5026003A
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English (en)
Japanese (ja)
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JPH05261296A (ja
Inventor
ジェイムズ・エドワード・バビン
デイビッド・ロバート・ブライアント
アーノルド・マイアロン・ハリソン
デイビッド・ジェイムズ・ミラー
Original Assignee
ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・テクノロジー・コーポレイション
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Publication of JPH05261296A publication Critical patent/JPH05261296A/ja
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Expired - Lifetime legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent
    • Y10S95/902—Molecular sieve

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Saccharide Compounds (AREA)
JP5026003A 1992-01-24 1993-01-22 ヒドロホルミル化触媒の再活性化 Expired - Lifetime JP2742860B2 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/825,083 US5237106A (en) 1992-01-24 1992-01-24 Reactivation of hydroformylation catalysts
US825083 1992-01-24

Publications (2)

Publication Number Publication Date
JPH05261296A JPH05261296A (ja) 1993-10-12
JP2742860B2 true JP2742860B2 (ja) 1998-04-22

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
JP5026003A Expired - Lifetime JP2742860B2 (ja) 1992-01-24 1993-01-22 ヒドロホルミル化触媒の再活性化

Country Status (22)

Country Link
US (1) US5237106A (ko)
EP (1) EP0552797B1 (ko)
JP (1) JP2742860B2 (ko)
KR (1) KR0131293B1 (ko)
CN (1) CN1074632A (ko)
AT (1) ATE136016T1 (ko)
AU (1) AU3196393A (ko)
BR (1) BR9300259A (ko)
CA (1) CA2087892A1 (ko)
CZ (1) CZ6893A3 (ko)
DE (1) DE69301930T2 (ko)
ES (1) ES2085060T3 (ko)
FI (1) FI930281A (ko)
HU (1) HUT66778A (ko)
MX (1) MX9300329A (ko)
NO (1) NO930219L (ko)
PL (1) PL170460B1 (ko)
RO (1) RO111739B1 (ko)
SA (1) SA93130348B1 (ko)
SK (1) SK2693A3 (ko)
TW (1) TW228480B (ko)
ZA (1) ZA93501B (ko)

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DE10005084C1 (de) * 2000-02-04 2001-09-13 Celanese Chem Europe Gmbh Verfahren zur Wiedergewinnung von Rhodium aus Reaktionsprodukten der Oxosynthese
GB0113079D0 (en) * 2001-05-30 2001-07-18 Kvaerner Process Tech Ltd Process
US7638039B2 (en) * 2004-06-15 2009-12-29 Cormetech, Inc. In-situ catalyst replacement
CN100526279C (zh) * 2006-04-11 2009-08-12 中国科学院兰州化学物理研究所 连续制备正戊醛的工艺过程
US7962486B2 (en) * 2008-01-10 2011-06-14 International Business Machines Corporation Method and system for discovery and modification of data cluster and synonyms
CN102950027B (zh) * 2011-08-30 2015-03-25 中国石油化工股份有限公司 用于羰基化反应的失活铑配合物催化剂的再生方法
CN102950028B (zh) * 2011-08-31 2015-02-25 中国石油化工股份有限公司 用于羰基化反应的失活铑膦配合物催化剂的再生方法
WO2013183796A1 (en) * 2012-06-04 2013-12-12 Lg Chem, Ltd. Hydroformylation method having improved catalyst stability in reaction
CN103506166B (zh) * 2012-06-27 2015-08-19 中国石油化工股份有限公司 失活铑膦催化剂的活化方法
CN103506167B (zh) * 2012-06-27 2015-08-19 中国石油化工股份有限公司 一种失活铑膦催化剂的处理方法
CN103769225B (zh) * 2012-10-22 2016-03-02 中国石油化工股份有限公司 羰基化反应失活或部分失活铑膦催化剂的再生方法
CN104045532B (zh) 2013-03-15 2018-05-25 陶氏技术投资有限责任公司 加氢甲酰化方法
CN104248994B (zh) * 2013-06-25 2018-03-20 中国石油化工股份有限公司 羰基化铑膦催化剂的活性恢复方法
CN104513143A (zh) 2013-09-26 2015-04-15 陶氏技术投资有限责任公司 加氢甲酰化方法
WO2019231611A1 (en) 2018-05-30 2019-12-05 Dow Technology Investments Llc Methods of controlling hydroformylation processes
JP2021525166A (ja) 2018-05-30 2021-09-24 ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー モノホスフィン、テトラホスフィン配位子の組み合わせを含む触媒組成物、およびそれを使用するヒドロホルミル化プロセス
JP2021525165A (ja) 2018-05-30 2021-09-24 ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー ヒドロホルミル化プロセスにおける触媒失活を遅らせるための方法、および／またはテトラホスフィン配位子の使用を遅らせるための方法
EP3990176A1 (en) 2019-06-27 2022-05-04 Dow Technology Investments LLC Process to prepare solution from hydroformylation process for precious metal recovery
TW202126385A (zh) * 2019-11-05 2021-07-16 美商陶氏科技投資有限公司 自氫甲醯化製程回收銠之方法
CN116685401A (zh) * 2020-09-25 2023-09-01 利安德化学技术有限公司 在加氢甲酰化中将乙烯与烯丙醇共进料以制备1,4-丁二醇和正丙醇
MX2023010493A (es) 2021-03-31 2023-09-18 Dow Technology Investments Llc Procesos de hidroformilacion.
WO2024129290A1 (en) 2022-12-13 2024-06-20 Dow Technology Investments Llc Process to minimize polyphosphine usage by making use of degradation products

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GB1219763A (en) * 1967-02-02 1971-01-20 Johnson Matthey & Company Improvements in catalytic hydrogenation or hydroformylation
US3555098A (en) * 1967-12-13 1971-01-12 Union Oil Co Hydroformylation
JPS5114482A (ja) * 1974-07-26 1976-02-04 Atsugi Kinzoku Kogyo Kk Kanguchiseizohoho
US4277627A (en) * 1977-01-25 1981-07-07 Union Carbide Corporation Hydroformylation process
EP0007768A3 (en) * 1978-07-27 1980-02-20 DAVY McKEE (LONDON) LIMITED Hydroformylation of alpha-olefinic compounds
US4297239A (en) * 1979-07-16 1981-10-27 Union Carbide Corporation Hydroformylation catalyst reactivation
JPS5633040A (en) * 1979-08-27 1981-04-03 Mitsubishi Chem Ind Ltd Activation of rhodium complex catalyst
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US4374278A (en) * 1980-02-28 1983-02-15 Union Carbide Corporation Hydroformylation catalyst reactivation
US4605780A (en) * 1980-09-24 1986-08-12 Union Carbide Corporation Reactivation of rhodium complex hydroformylation catalysts
JPS5923858B2 (ja) * 1981-01-22 1984-06-05 三菱化学株式会社 ロジウム錯体の取得方法
DE3534314A1 (de) * 1985-09-26 1987-04-02 Ruhrchemie Ag Verfahren zur herstellung von aldehyden
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US4929767A (en) * 1988-08-12 1990-05-29 Union Carbide Chemicals And Plastics Company Inc. Treatment of rhodium catalysts
US4861918A (en) * 1988-08-12 1989-08-29 Union Carbide Corporation Reactivation of hydroformylation catalysts
US4950629A (en) * 1988-12-27 1990-08-21 Eli Lilly And Company Process for catalyst recovery
US5183943A (en) * 1991-03-18 1993-02-02 Union Carbide Chemicals & Plastics Technology Corporation Reactivation of hydroformylation catalysts

Also Published As

Publication number Publication date
TW228480B (ko) 1994-08-21
EP0552797A1 (en) 1993-07-28
HUT66778A (en) 1994-12-28
ES2085060T3 (es) 1996-05-16
ATE136016T1 (de) 1996-04-15
BR9300259A (pt) 1993-08-24
FI930281A (fi) 1993-07-25
DE69301930T2 (de) 1996-10-02
PL297519A1 (en) 1993-08-23
EP0552797B1 (en) 1996-03-27
SK2693A3 (en) 1993-11-10
NO930219L (no) 1993-07-26
FI930281A0 (fi) 1993-01-22
DE69301930D1 (de) 1996-05-02
AU3196393A (en) 1993-07-29
PL170460B1 (pl) 1996-12-31
RO111739B1 (ro) 1997-01-30
KR0131293B1 (ko) 1998-04-14
JPH05261296A (ja) 1993-10-12
US5237106A (en) 1993-08-17
SA93130348B1 (ar) 2005-07-02
HU9300185D0 (en) 1993-04-28
MX9300329A (es) 1994-06-30
KR930016146A (ko) 1993-08-26
CA2087892A1 (en) 1993-07-25
NO930219D0 (no) 1993-01-22
ZA93501B (en) 1993-08-25
CZ6893A3 (en) 1993-10-13
CN1074632A (zh) 1993-07-28

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